CN111848861B - Response type hydrogel based on coordination of organic tellurium and platinum and preparation method - Google Patents
Response type hydrogel based on coordination of organic tellurium and platinum and preparation method Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 113
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 107
- 239000000017 hydrogel Substances 0.000 title claims abstract description 77
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 65
- 230000004044 response Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000084 colloidal system Substances 0.000 claims abstract description 44
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- -1 platinum ions Chemical class 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 42
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical group OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 6
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 3
- 229960003180 glutathione Drugs 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 12
- 230000004043 responsiveness Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 230000001960 triggered effect Effects 0.000 abstract description 3
- 239000002265 redox agent Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YGMQDBCXHASOHO-UHFFFAOYSA-N 3-bromopropan-1-amine;hydrochloride Chemical compound Cl.NCCCBr YGMQDBCXHASOHO-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Preparation (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a response type hydrogel based on coordination of organic tellurium and platinum and a preparation method thereof, wherein organic tellurium and acrylamide monomer aqueous solution are mixed, hydrogel containing organic tellurium is obtained under the action of an initiator, then platinum ions are added, tellurium can coordinate with platinum to form hydrogel with larger mechanical strength, then an oxidant is added into colloid to oxidize organic tellurium, so that the coordination of organic tellurium and platinum disappears, a reducing agent is added to reduce and oxidize organic tellurium, the coordination of organic tellurium and platinum is recovered, and redox response can be carried out on organic tellurium. The invention has simple operation process, lower cost and redox response characteristic. The hydrogel with redox reversible responsiveness based on coordination of organic tellurium and platinum can realize the change of mechanical strength in different degrees, the change of mechanical strength is closely related to redox agents, and the hydrogel has the characteristic of redox-triggered mechanical strength change.
Description
Technical Field
The invention belongs to the field of hydrogel, and particularly relates to response type hydrogel based on coordination of organic tellurium and platinum and a preparation method thereof.
Background
The hydrogel is a material with a three-dimensional network structure formed by macromolecules through physical or chemical action, and has the characteristics of high water content, good permeability and the like. The traditional hydrogel is insensitive to the change of the surrounding environment and has no irritation response. In recent years, intelligent hydrogel has received more and more attention due to its physicochemical properties to respond to external stimuli and to realize multiple functions.
Tellurium is in the same family as oxygen, sulfur, selenium. Research in organic tellurium chemistry can go up to 1840,
the first organic telluride, dialkyl tellurium, is synthesized. More and more researches show that organic tellurium-containing molecules have a certain protection effect on existing organisms. The radius of tellurium atom is larger than that of sulfur atom and selenium atom, and the electronegativity of tellurium is weaker than that of sulfur and selenium. According to the scale of pallin, the method of the invention,the electronegativity of sulfur is 2.58, that of selenium is 2.55, and that of tellurium is only 2.10, so tellurium has a lower redox potential. By utilizing the characteristic of low oxidation-reduction potential of tellurium, a tellurium-containing polymer aggregate with sensitive oxidation-reduction responsiveness is prepared and is used for in vivo targeted delivery of a medicament. In addition, the organic tellurium compound can be used as a ligand of platinum ions, and the complex has sensitive redox responsiveness. Currently, the redox properties of organic tellurium are gaining increasing attention and application.
Disclosure of Invention
The invention aims to introduce organic tellurium molecules into a hydrogel system, and provides a hydrogel with redox responsiveness based on coordination of organic tellurium and platinum based on coordination of tellurium and platinum.
The second purpose of the invention is to provide a preparation method of the reversible redox responsive hydrogel based on coordination of organic tellurium and platinum, which has simple preparation process and is green and environment-friendly.
The technical scheme of the invention is summarized as follows:
a preparation method of reversible redox-responsive hydrogel based on coordination of organic tellurium and platinum comprises the steps of mixing organic tellurium and an acrylamide monomer aqueous solution, obtaining hydrogel containing organic tellurium under the action of an initiator, adding platinum ions, enabling tellurium to be coordinated with platinum to form hydrogel with high mechanical strength, adding an oxidant into colloid, oxidizing organic tellurium, enabling coordination of organic tellurium and platinum to disappear, adding a reducing agent, reducing and oxidizing organic tellurium, and recovering coordination of organic tellurium and platinum, namely performing redox response on organic tellurium.
The mass concentration of the aqueous solution of the acrylamide monomer is 5-80%, the mass concentration of the organic solution of the synthesized tellurium-containing monomer is 1-30%, and the volume ratio of the mass concentration of the aqueous solution of the acrylamide monomer to the mass concentration of the organic solution of the synthesized tellurium-containing monomer is (5-1) to (80-1).
The initiator induces a radical, and is a thermal decomposition type initiator (such as azobisisobutyronitrile), a redox type initiator (such as dibenzoyl peroxide, ammonium persulfate), or a photolysis type initiator (such as IRGACURE 2100). The tellurium-containing monomer is a tellurium-containing organic molecule with one end containing a carbon-carbon double bond or two ends containing carbon-carbon double bonds.
The acrylamide monomer is acrylamide, N-hydroxyethyl acrylamide or N-isopropyl acrylamide.
The platinum ions are platinum-containing solutions capable of coordinating with organic tellurium.
The oxidizing agent and the reducing agent are agents that can oxidize or reduce organic tellurium. The ratio of the amount of substance added to the organic tellurium is (1-10) to (10-1).
The oxidizing agent can be but is not limited to hydrogen peroxide, sodium hypochlorite, peroxyacetic acid, and the reducing agent can be but is not limited to glutathione, ascorbic acid, sodium borohydride.
The hydrogel with redox reversible responsiveness based on coordination of organic tellurium and platinum is prepared by the method.
The invention has the beneficial effects that: the method adopts a green and environment-friendly one-step synthesis method to prepare the hydrogel which is based on coordination of organic tellurium and platinum and has redox reversible responsiveness, and has the advantages of simple and convenient operation process, lower cost and redox response characteristic. The design principle of the invention is to fully utilize the low oxidation-reduction potential of tellurium, increase the crosslinking degree of colloid by coordinating organic tellurium and platinum, increase the mechanical strength of the colloid, oxidize organic tellurium by an oxidant, eliminate the coordination of organic tellurium and platinum, and add a reducing agent to recover the coordination of organic tellurium and platinum, thereby preparing the hydrogel with redox reversibility. According to the hydrogel with redox reversible responsiveness based on coordination of organic tellurium and platinum, which is prepared by the invention, the low redox potential of tellurium endows the hydrogel with redox triggered mechanical strength change characteristics, and according to different redox conditions, the hydrogel with redox reversible responsiveness based on coordination of organic tellurium and platinum can realize mechanical strength change of different degrees, and the mechanical strength change is closely related to redox agents and has the characteristics of redox triggered mechanical strength change.
Drawings
FIG. 1 is a digital photograph of a hydrogel formed from the tellurium-containing monomer and an acrylamide-based monomer prepared in example 1;
FIG. 2 is a digital photograph of a hydrogel formed of the tellurium-containing monomer, the acrylamide-based monomer, and platinum prepared in example 1;
FIG. 3 is a digital photograph of a hydrogel formed from the tellurium-containing monomer, the acrylamide-based monomer, platinum and the oxidant prepared in example 1;
FIG. 4 is a digital photograph of a hydrogel formed from the tellurium-containing monomer, the acrylamide-based monomer, platinum, the oxidizing agent and the reducing agent prepared in example 1;
FIG. 5 is a rheological diagram of a hydrogel formed from the tellurium-containing monomer and an acrylamide-based monomer prepared in example 1;
FIG. 6 is a rheological diagram of a hydrogel formed from tellurium-containing monomers, acrylamide-based monomers and platinum prepared in example 1;
FIG. 7 is a rheological diagram of a hydrogel formed from tellurium-containing monomers, acrylamide-based monomers, platinum and an oxidizing agent prepared in example 1;
FIG. 8 is a rheological diagram of a hydrogel-forming polymer of the tellurium-containing monomer prepared in example 1, an acrylamide-based monomer, platinum, an oxidizing agent and a reducing agent.
FIG. 9 shows a hydrogel of Te-containing monomer, acrylamide-based monomer and Pt prepared in example 1, sequentially added to a colloid
A rheogram of cyclically adding an oxidant and a reductant.
The specific implementation mode is as follows:
the invention will be further described by means of specific embodiments with reference to the accompanying drawings.
EXAMPLE 1 preparation of tellurium-containing monomers
Taking a tellurium-containing monomer with carbon-carbon double bonds at two ends as an example, the preparation of the tellurium-containing monomer is introduced, and the method comprises the following steps: tellurium powder and sodium borohydride react in water phase; after adding 3-bromopropylamine hydrochloride aqueous solution, the mixture was stirred overnight at 50 ℃ under a nitrogen atmosphere. Extracting the product by dichloromethane, washing by sodium hydroxide solution, dehydrating and drying by anhydrous magnesium sulfate, and performing rotary evaporation on the organic phase to obtain the product. Dissolving the product in water phase, adding triethylamine, adding methacrylic acid chloride dissolved in tetrahydrofuran into the solution, and stirring overnight at normal temperature under nitrogen atmosphere. Extracting the product by dichloromethane, washing by sodium chloride solution, dehydrating and drying by anhydrous magnesium sulfate, and carrying out rotary evaporation on the organic phase to obtain the product of the tellurium-containing monomer with carbon-carbon double bonds at two ends.
The tellurium-containing monomer having a carbon-carbon double bond at one end can also be prepared by the above-mentioned method (i.e., by adjusting the amount of methacryloyl chloride to be added, and the rest being as described above). The above method is disclosed in order to enable those skilled in the art to practice the method, but the present invention is not limited thereto, and tellurium-containing monomers having a carbon-carbon double bond at one end or both ends prepared by other methods may be used in the present invention.
Example 2
A preparation method of redox reversible responsive hydrogel based on coordination of organic tellurium and platinum comprises the following steps:
(1) respectively preparing 10% of N-hydroxyethyl acrylamide aqueous solution and 1% of tellurium-containing monomer with carbon-carbon double bonds at two ends;
(2) mixing an aqueous solution of N-hydroxyethyl acrylamide with the mass concentration of 10% with a tellurium-containing monomer with the mass concentration of 1% and carbon-carbon double bonds at two ends according to the volume ratio of 2:1, and initiating by an initiator ammonium persulfate to form the hydrogel containing organic tellurium.
The hydrogel prepared in this example was a translucent solid hydrogel in daylight (fig. 1), after which platinum ions were added to the colloid, and the platinum ions completely penetrated into the hydrogel, which turned into a yellow solid hydrogel (fig. 2). After adding the oxidant hydrogen peroxide (50mM, 100. mu.L) to the colloid, the hydrogel turned into a pale yellow solid hydrogel (FIG. 3), and then adding the reductant ascorbic acid (50mM, 100. mu.L) to the colloid, the hydrogel turned into a black hydrogel (FIG. 4). The hydrogel showed an increase in mechanical strength upon addition of platinum ions, as can be seen by rheological testing (FIGS. 5-8); after the oxidant is added, the mechanical strength of the colloid is reduced; after the reducing agent is added, the mechanical strength of the colloid is increased, and the colloid has redox responsiveness.
By cyclically adding the oxidizing agent and the reducing agent to the colloid, the organotellurium is cyclically oxidized and reduced, the mechanical strength of the colloid is cyclically increased, and the colloid can reversibly perform an oxidation-reduction response (fig. 9).
Example 3
A preparation method of redox reversible responsive hydrogel based on coordination of organic tellurium and platinum comprises the following steps:
(1) respectively preparing 5% acrylamide aqueous solution and 1% tellurium-containing monomer with carbon-carbon double bonds at two ends;
(2) mixing 5% acrylamide aqueous solution and 1% tellurium-containing monomer with carbon-carbon double bonds at two ends according to the volume ratio of 2:1, and initiating by an initiator IRGACURE2100 to form organic tellurium-containing hydrogel.
(3) Platinum ions are then added to the colloid, and the hydrogel becomes a yellow solid hydrogel after the platinum ions completely penetrate into the hydrogel, so that the mechanical strength of the colloid is increased. Then, sodium hypochlorite (50mM, 52.6. mu.L) as an oxidant was added to the colloid, whereby the coordination of the organotellurium to platinum disappeared and the mechanical strength of the colloid decreased. Sodium borohydride (50mM, 52.6. mu.L) was added as a reducing agent to the gel, and the hydrogel turned into a black hydrogel, which increased the mechanical strength of the gel.
By cyclically adding the oxidizing agent and the reducing agent to the colloid, the organotellurium is cyclically oxidized and reduced, the mechanical strength of the colloid is cyclically increased, and the colloid can reversibly perform an oxidation-reduction response.
Example 4
A preparation method of redox reversible responsive hydrogel based on coordination of organic tellurium and platinum comprises the following steps:
(1) respectively preparing an acrylamide aqueous solution with the mass concentration of 80 percent and tellurium-containing monomers with carbon-carbon double bonds at two ends with the mass concentration of 30 percent;
(2) mixing 5% of acrylamide aqueous solution with 30% of tellurium-containing monomer with carbon-carbon double bonds at two ends according to the volume ratio of 2:1, and initiating by an initiator IRGACURE2100 to form organic tellurium-containing hydrogel.
(3) Platinum ions are then added to the colloid, and the hydrogel becomes a yellow solid hydrogel after the platinum ions completely penetrate into the hydrogel, so that the mechanical strength of the colloid is increased. Then sodium hypochlorite (10mM, 79 μ L) is added into the colloid, so that the coordination of the organic tellurium and the platinum disappears, and the mechanical strength of the colloid is reduced. Sodium borohydride (10mM, 79. mu.L) was added as a reducing agent to the gel, and the hydrogel turned into a black hydrogel, which increased the mechanical strength of the gel.
By cyclically adding the oxidizing agent and the reducing agent to the colloid, the organotellurium is cyclically oxidized and reduced, the mechanical strength of the colloid is cyclically increased, and the colloid can reversibly perform an oxidation-reduction response.
Example 5
A preparation method of redox reversible responsive hydrogel based on coordination of organic tellurium and platinum comprises the following steps:
(1) respectively preparing 10% mass concentration N-isopropyl acrylamide aqueous solution and 1% mass concentration tellurium-containing monomer with carbon-carbon double bonds at two ends;
(2) mixing 10% of N-isopropyl acrylamide aqueous solution with 1% of tellurium-containing monomer with carbon-carbon double bonds at two ends according to the volume ratio of 2:1, and initiating by an initiator such as azobisisobutyronitrile to form organic tellurium-containing hydrogel.
(3) Platinum ions are then added to the colloid, and the hydrogel becomes a yellow solid hydrogel after the platinum ions completely penetrate into the hydrogel, so that the mechanical strength of the colloid is increased. The colloid was then added with peroxyacetic acid (50mM, 100. mu.L) as an oxidant, and the coordination of organotellurium to platinum disappeared, and the mechanical strength of the colloid decreased. Glutathione (50mM, 100. mu.L) is added into the colloid as a reducing agent, the hydrogel is changed into black hydrogel, and the mechanical strength of the colloid is increased.
By cyclically adding the oxidizing agent and the reducing agent to the colloid, the organotellurium is cyclically oxidized and reduced, the mechanical strength of the colloid is cyclically increased, and the colloid can reversibly perform an oxidation-reduction response.
Example 6
A preparation method of redox reversible responsive hydrogel based on coordination of organic tellurium and platinum comprises the following steps:
(1) respectively preparing 10% of aqueous solution of N-hydroxyethyl acrylamide and 1% of tellurium-containing monomer with carbon-carbon double bond at one end;
(2) mixing an aqueous solution of N-hydroxyethyl acrylamide with the mass concentration of 10% with a tellurium-containing monomer with the mass concentration of 1% and a carbon-carbon double bond at one end according to the volume ratio of 2:1, and initiating by an initiator ammonium persulfate to form a solution containing organic tellurium.
(3) Platinum ions are then added to the solution and the solution turns into a yellow solid hydrogel as platinum ions fully penetrate into the solution. Then, hydrogen peroxide (50mM, 100. mu.L) as an oxidizing agent was added to the colloid, whereby the coordination of the organotellurium to platinum disappeared and the colloid became a solution. Then, ascorbic acid (50mM, 100. mu.L) was added as a reducing agent to the colloid, and the solution state was changed to a colloid state.
By cyclically adding the oxidizing agent and the reducing agent to the colloid, the organotellurium is cyclically redox, and the solution and the colloid state can be reversibly circulated.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A preparation method of response type hydrogel based on coordination of organic tellurium and platinum is characterized in that a synthesized organic solution containing tellurium monomers is mixed with an acrylamide type monomer aqueous solution, organic tellurium-based hydrogel is obtained under the action of an initiator, platinum ions are added, organic tellurium and platinum are coordinated to form hydrogel with high mechanical strength, then an oxidant and a reducing agent are added into a colloid, and tellurium is reversibly oxidized and reduced to obtain hydrogel with the redox response type characteristic based on tellurium; the tellurium-containing monomer is a tellurium-containing organic molecule with one end containing a carbon-carbon double bond or two ends containing carbon-carbon double bonds; the acrylamide monomer is acrylamide, N-hydroxyethyl acrylamide or N-isopropyl acrylamide; the mass concentration of the aqueous solution of the acrylamide monomer is 5-80%, the mass concentration of the synthesized organic solution containing the tellurium monomer is 1-30%, and the volume ratio of the aqueous solution of the acrylamide monomer with the mass concentration to the synthesized organic solution containing the tellurium monomer with the mass concentration is (5-1): 80-1.
2. The method for preparing responsive hydrogel based on coordination of organic tellurium and platinum according to claim 1, characterized in that the initiator is thermal decomposition type initiator.
3. The method for preparing the organotellurium-platinum coordination based responsive hydrogel according to claim 1, wherein the initiator is a redox initiator.
4. The method for preparing responsive hydrogel based on coordination of organic tellurium and platinum as claimed in claim 1, wherein the initiator is photodecomposition type initiator.
5. The method for preparing responsive hydrogel based on coordination of organic tellurium and platinum as claimed in claim 1, wherein the platinum ion is platinum-containing solution capable of coordinating with organic tellurium.
6. The method for preparing responsive hydrogel based on coordination of organic tellurium and platinum as claimed in claim 1, wherein the oxidant and the reductant are capable of oxidizing or reducing organic tellurium, and the ratio of the added substance amount of the oxidant or the reductant to the substance amount of the organic tellurium is (1-10): (10-1).
7. The method for preparing the response type hydrogel based on coordination of organic tellurium and platinum as claimed in claim 6, wherein the oxidant is hydrogen peroxide, sodium hypochlorite and peroxyacetic acid, and the reducing agent is glutathione, ascorbic acid and sodium borohydride.
8. Responsive hydrogels based on organotellurium complexed with platinum prepared by the process of any one of claims 1 to 7.
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| CN105287362A (en) * | 2015-11-13 | 2016-02-03 | 复旦大学 | Thermally induced hydrogel containing selenium or tellurium, and preparation method and applications thereof |
| CN105745230A (en) * | 2013-11-27 | 2016-07-06 | 日本瑞翁株式会社 | Radical polymerization initiator and method for producing polymers |
| CN107033372A (en) * | 2017-05-15 | 2017-08-11 | 暨南大学 | Hydrogel with multiple response function and its production and use |
| CN108137728A (en) * | 2015-10-02 | 2018-06-08 | 三大雅株式会社 | Water-absorbent besin particles and its manufacturing method |
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| CN105745230A (en) * | 2013-11-27 | 2016-07-06 | 日本瑞翁株式会社 | Radical polymerization initiator and method for producing polymers |
| CN108137728A (en) * | 2015-10-02 | 2018-06-08 | 三大雅株式会社 | Water-absorbent besin particles and its manufacturing method |
| CN105287362A (en) * | 2015-11-13 | 2016-02-03 | 复旦大学 | Thermally induced hydrogel containing selenium or tellurium, and preparation method and applications thereof |
| CN107033372A (en) * | 2017-05-15 | 2017-08-11 | 暨南大学 | Hydrogel with multiple response function and its production and use |
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